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Asymmetric Reactions Enabled by Cooperative Enantioselective Amino- and Lewis Acid Catalysis

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Abstract

Organocatalysis—the branch of catalysis featuring small organic molecules as the catalysts—has, in the last decade, become of central importance in the field of asymmetric catalysis, so much that it is now comparable to metal catalysis and biocatalysis. Organocatalysis is rationalized and classified by a number of so-called activation modes, based on the formation of a covalent or not-covalent intermediate between the organocatalyst and the organic substrate. Among all the organocatalytic activation modes, enamine and iminium catalysis are widely used for the practical preparation of valuable products and intermediates, both in academic and industrial contexts. In both cases, chiral amines are employed as catalysts. Enamine activation mode is generally employed in the reaction with electrophiles, while nucleophiles require the iminium activation mode. Commonly, in both modes, the reaction occurs through well-organized transitions states. A large variety of partners can react with enamines and iminium ions, due to their sufficient nucleophilicity and electrophilicity, respectively. However, despite the success, organocatalysis still suffers from narrow scopes and applications. Multicatalysis is a possible solution for these drawbacks because the two different catalysts can synergistically activate the substrates, with a simultaneous activation of the two different reaction partners. In particular, in this review we will summarize the reported processes featuring Lewis acid catalysis and organocatalytic activation modes synergically acting and not interfering with each other. We will focus our attention on the description of processes in which good results cannot be achieved independently by organocatalysis or Lewis acid catalysis. In these examples of cooperative dual catalysis, a number of new organic transformations have been developed. The review will focus on the possible strategies, the choice of the Lewis acid and the catalytic cycles involved in the effective reported combination. Additionally, some important key points regarding the rationale for the effective combinations will be also included. π-Activation of organic substrates by Lewis acids, via formation of electrophilic intermediates, and their reaction with enamines will be also discussed in this review.

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Acknowledgements

The authors kindly thank Letizia Vanni d’Archirafi and Benedetta Gaggio for their suggestions to improve the readability of this review. The authors also want to thank the reviewers for their valuable advices to improve the scientific quality of this review.

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Authors and Affiliations

  1. Dipartimento di Chimica “G. Ciamician”, Alma Mater Studiorum, Università di Bologna, Via Selmi 2, Bologna, Italy

    Pier Giorgio Cozzi, Andrea Gualandi, Francesco Calogero & Giacomo Rodeghiero

  2. Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126, Pisa, Italy

    Simone Potenti

  3. Cyanagen Srl, Via Stradelli Guelfi 40/C, 40138, Bologna, Italy

    Giacomo Rodeghiero

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  1. Pier Giorgio Cozzi
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  2. Andrea Gualandi
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  4. Francesco Calogero
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  5. Giacomo Rodeghiero
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Correspondence to Pier Giorgio Cozzi.

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This article is part of the Topical Collection “Asymmetric Organocatalysis Combined with Metal Catalysis”; edited by Bruce A. Arndtsen, Liu-Zhu Gong.

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Cozzi, P.G., Gualandi, A., Potenti, S. et al. Asymmetric Reactions Enabled by Cooperative Enantioselective Amino- and Lewis Acid Catalysis. Top Curr Chem (Z) 378, 1 (2020). https://doi.org/10.1007/s41061-019-0261-4

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